CN103755523B - A kind of preparation method of 2-methallyl alcohol - Google Patents
A kind of preparation method of 2-methallyl alcohol Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- C07—ORGANIC CHEMISTRY
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
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Abstract
The preparation method of a kind of 2-methallyl alcohol provided by the invention, comprises the following steps: under catalyst A, water vapour and air exist, iso-butylene is oxidized to 2-methallyl aldehyde; Under catalyst B, hydrogen exist, 2-methacrylic aldehyde is reduced to 2-methallyl alcohol.The method, taking iso-butylene as starting raw material, is methallyl aldehyde by metal oxide selective oxidation, and then the method that hydrogenation reaction produces 2-methallyl alcohol directly occurs, productive rate is high, cost is low, energy consumption is little, environment-protecting clean.
Description
Technical field
The present invention relates to a kind of environment-friendly preparation method thereof of 2-methallyl alcohol, belong to field of chemical technology.
Background technology
2-methallyl alcohol (having another name called metallyl alcohol, isobutene alcohol or methallyl alcohol), be a kind of unsaturated alcohol, colourless liquid, has irritating smell.It, as a kind of very important organic intermediate, can be used as polymer monomer, resin and spices, also can make initiator, synthesizes corresponding methacrylic acid and corresponding ester.Its most important purposes is synthesizing methyl allyl polyethenoxy ether.Methacrylic Soxylat A 25-7 is the important monomer of synthesis forth generation polycarboxylic acid series water reducing agent, and it can have decisive action for high efficiency such as polycarboxylate water-reducer low-dosage, high diminishing, low slumps.The application of methacrylic Soxylat A 25-7 can make the mobility of concrete mix and flowing retentivity is good, loss of slump is low, effect enhancing potentiality are large, shrinking percentage is low, thus make that the purposes of polycarboxylate water-reducer is more extensive, adaptability is stronger, can be applicable to the field that water conservancy, nuclear power engineering etc. are important.12 planning ends, the demand of concrete admixture field only methacrylic Soxylat A 25-7 will reach 23.06 ten thousand tons, and 2-methallyl alcohol annual requirement is 1.0 ten thousand tons when the time comes, wide market.In addition, 2-methallyl alcohol can also synthesize containing allylic ester with other organic acid, therefore 2-methallyl alcohol has important application in the initiator of concrete admixture polyether macromonomer, the field such as polymerization single polymerization monomer and tensio-active agent, the research of its preparation method has larger economic benefit and social benefit.
With 2-methallyl chloride for starting raw material, adopting alkaline water solution to produce 2-methallyl alcohol is the industrial method developed the earliest.
Patent US2072015, US2323781, US2313767 and JP2009107949 have mainly carried out Improvement and perfection around direct hydrolysis method.But because the activity of methylallyl chloride is more weak, usually need to add highly basic and organic solvent during hydrolysis, and react and could must react under higher temperature of reaction and pressure, severe reaction conditions, yield are lower, organic solvent is difficult to recovery; In addition, the growing amount of by product ether is also comparatively large, and industry is purified comparatively difficult.Wherein, patent US2313767 reports the method for carrying out chlorallylene hydrolysis at a lower temperature and preparing vinyl carbinol, adopts cylindrical reactor, and arranges condenser low temperature recovery chlorallylene, but reaction efficiency is lower; Wherein, Japanese Patent JP2009107949 uses DMF facilitation of hydrolysis in order to avoid using heavy metal catalyst, and this reaction process will introduce reluctant DMF solvent, causes certain pollution to environment.
Patent CN101759528 discloses the direct hydrolysis method synthesis 2-methallyl alcohol of the methylallyl chloride adopting Catalyzed by Polyethylene Glycol.But the alkali lye system circulation that the method uses is complicated, and the catalytic efficiency of polyoxyethylene glycol is lower, and the yield of its single reaction is not high; In addition, production unit and energy consumption are comparatively large, do not meet the green idea of current energy-saving and emission-reduction.
The main drawback of above-mentioned direct hydrolysis method is that the side reaction such as etherificate, esterification easily occurs, and causes reaction efficiency not high, and requires the low concentration solution adding highly basic, and the wastewater flow rate of discharge is large, and energy consumption is high.
With 2-methallyl chloride for starting raw material, adopting esterification catalysis two-step approach to produce 2-methallyl alcohol is current most widely used industrial method.
Patent CN103242139A discloses the technique of esterification catalysis two-step approach, have employed functional group's switch technology of organic synthesis, first synthesize 2-methallyl alcohol carboxylicesters, and then the highly basic adding lower concentration is hydrolyzed, although add synthesis step, but the functional group between compound is easy to conversion, and combined reaction efficiency is higher.But, although the program improves reaction efficiency, need to add carboxylic acid sodium, highly basic and phase-transfer catalyst, cause reacting producing a large amount of abraum salt, waste water.
With 2-methallyl aldehyde for starting raw material, the method adopting hydro-reduction reaction to produce 2-methallyl alcohol merits attention.US Patent No. 2779801, US2713074 and Japanese Patent JP-B56-36176 disclose and adopt aluminium alcoholates to be the reduction reaction of catalyzer, and temperature, pressure are all lower, and reaction conversion ratio and selectivity all can reach more than 90%, but Virahol demand is larger; US Patent No. 2767221 and US4731488 report the gas phase hydrogen transfer reactions that the polynary double oxide MgXYO based on MgO is catalyzer, the selectivity of acrolein conversion rate and vinyl carbinol reaches 90% and 92% respectively, but temperature of reaction is higher, catalyst preparing needs high-temperature calcination; Domestic patent CN102167657 also reports with 2-methallyl aldehyde to be starting raw material catalytic hydrogen reduction technique prepares 2-methallyl alcohol, but starting raw material 2-methallyl aldehyde needed for the program is unstable, is difficult to preserve and long-time transport.
In sum, larger for traditional technology (direct hydrolysis method and esterification catalysis two-step approach) that starting raw material prepares 2-methallyl alcohol generally exists highly basic, water or consumption of organic solvent with 2-methallyl chloride, and be difficult to reclaim, the deficiencies such as this result also in, and production cost is high, energy consumption is high, Industrial " three Waste " discharge is more; With 2-methallyl aldehyde for the technique of starting raw material synthesis unsaturated alcohol represents synthesis technique of new generation, but need to add powerful catalyst and operational path research.
Summary of the invention
Goal of the invention: the object of the present invention is to provide that a kind of productive rate is high, cost is low, energy consumption is little, the environment-friendly preparation method thereof of the 2-methallyl alcohol of environment-protecting clean.
Technical scheme: the preparation method of a kind of 2-methallyl alcohol provided by the invention, comprises the following steps:
(1) under catalyst A, water vapour and air exist, iso-butylene is oxidized to 2-methallyl aldehyde;
(2) under catalyst B, hydrogen exist, 2-methacrylic aldehyde is reduced to 2-methallyl alcohol.
Its synthetic route is:
In step (1), the existence of vapor atmosphere is very crucial to oxidizing reaction, and the volume ratio of described iso-butylene, water vapor and air is (4:4:92) ~ (8:8:84).
In step (1), oxidizing reaction temperature is 320 ~ 380 DEG C, and oxidizing reaction air speed is 3000 ~ 6000h
-1.
In step (1), described catalyst A is Mo-Bi system complex oxide, and its structural formula can be expressed as: Mo
a-Bi
b-M
iI c-M
iII d-M
i e-X
f-O
g;
Wherein,
M
iIbe selected from Ni
2+, Co
2+, Mg
2+, Mn
2+, Cu
2+and Pb
2+in 1 to 3 kind;
M
iIIbe selected from Fe
3+, Cr
3+, Al
3+in 1 to 3 kind;
M
ibe selected from K
+, Na
+, Cs
+, Tl
+deng 1 to 3 in alkalimetal ion kind;
X is P or B;
Wherein, a, b, c, d, e, f, g represent the atomic ratio of often kind of element respectively, a=12+ (1.6 ~ 4.0), b=0.1 ~ 0.8, c=5 ~ 8, d=1.0 ~ 2.8, e=0 ~ 0.4, f=0 ~ 0.4, and g is the numerical value meeting other element oxide state;
The preparation method of catalyst A can adopt art methods, be specially: by nitrate ultrasonic 10 ~ 30min in water solution system of ammonium molybdate and respective element, after fully mixing, namely co-precipitation obtains (see: petrochemical complex, 2008,37,1133 or patent CN101088608A).
In step (2), the existence of liquid water is very crucial to reduction reaction, and the volume ratio of described 2-methallyl aldehyde and water is 0.8 ~ 1.2.
In step (2), reduction reaction temperature is 60 ~ 90 DEG C, reduction reaction system pressure 0.4 ~ 1.0MPa, reduction reaction air speed 3 ~ 6h
-1.
In step (2), the structural formula of described catalyst B is M-ReOx/SiO
2-n;
Wherein,
M is selected from 1 to 2 kind in Ir, Rh, Pd, Ru and Pt; Preferred M be selected from Ir and Rh one or both;
N represents Re/M value, n=0.8 ~ 1.2; The oxidation state of x representative element Re.
The preparation method of catalyst B can adopt art methods, see: Chem.Commun., 2013,49,7034; Appl.Catal., B, 2011,105,117.
Beneficial effect: the preparation method of a kind of 2-methallyl alcohol provided by the invention, take iso-butylene as starting raw material, be methallyl aldehyde by metal oxide selective oxidation, then directly there is the method that hydrogenation reaction produces 2-methallyl alcohol, catalytic reaction efficiency is high, selectivity good, concise in technology, low, the environmental friendliness of lowering consumption, is easy to realize industrialization scale operation.
Specifically, the present invention, relative to prior art, has following outstanding advantage:
(1) the inventive method adopts with petrochemical complex C4 main fraction-iso-butylene as industrial raw material, directly prepare 2-methallyl alcohol by continuous print redox reaction, with tradition with 2-methallyl chloride for raw material carry out esterification catalysis two-step approach or direct hydrolysis method synthesize to have compared with target product " Atom economy ", environmentally friendly, react clean, the advantage such as to discharge without " three industrial wastes ".
(2) the catalyzer long service life that uses of the inventive method, in fixed-bed reactor can continuous catalytic reaction more than 2000 hours and reaction yield without obvious reduction, greatly reduce cost, be easy to industrialization scale operation.
(3) catalyst efficiency that uses of the inventive method is high, reaction preference is high, and the sufficient material of unreacted can circulating reaction, and product aftertreatment is simple, only need simple rectifying more than 98% sterling.
(4) the inventive method new technology, succinct, equipment only needs two fixed-bed reactor of connect and corollary system just can realize, and cost of investment is low.
Accompanying drawing explanation
Fig. 1 is the hydrogen spectrogram of 2-methallyl alcohol.
Fig. 2 is the mass spectrum of 2-methallyl alcohol.
Fig. 3 is a kind of process flow diagram of continuous prodution 2-methallyl alcohol.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, concrete material proportion, processing condition and result thereof described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
The raw material iso-butylene that the present invention uses is industrial raw material, and iso-butylene purity should be more than 98.0%.
Embodiment 1
The preparation method of 2-methallyl alcohol, is shown in Fig. 3, comprises the following steps:
(1) under room temperature 25 DEG C of conditions, by iso-butylene: water vapour: the volume ratio charging of air=6:6:88, Feed space velocities 4000h
-1, the catalyst A molecular formula of fixed-bed reactor filling is: Mo
13.6bi
0.6co
6fe
1.8cs
0.2b
0.2o
g, temperature of reaction is 360 DEG C, and reactor thief hole samples, gas chromatographic detection, when iso-butylene≤0.1%, 2-methallyl aldehyde>=98.0%, shows to react completely, discharging enters condenser, gas-liquid separator successively, and the aqueous solution of isolated 2-methallyl aldehyde enters next step reaction unit;
(2) plant hydrogen first purges the fixed-bed reactor being filled with catalyst B, catalyst B molecular formula: Ir-ReOx/SiO
2-1, the then aqueous solution of charging 2-methallyl aldehyde, the volume ratio controlling methacrolein and water is 1.2, is filled with H in plant hydrogen to reactor
2pressure keeps 0.8MPa, keeps air speed 4h
-1temperature of reaction 80 DEG C, gas chromatographic detection, 2-methallyl aldehyde≤0.1%, 2-methallyl alcohol>=98.0%, show to react completely, material enters condenser, gas-liquid separator, isolated hydrogen circulates, liquid material is pumped to the rectifying tower that 16 pieces of stage number are housed and purifies, and is slowly warming up to 150 DEG C, keeps reflux ratio 1.5, selection 100 ~ 120 DEG C, the content of 2-methallyl alcohol can reach 99%, comprehensively accounts, and the yield of two-step reaction 2-methallyl alcohol is 89%, selection rate is 93%.
Product characterizes, and hydrogen spectrum is shown in Fig. 1, and gas-chromatography is shown in Fig. 2.
1HNMR(CDCl
3,25℃,TMS),δ=1.74(s,3H,-CH
3),1.86(s,1H,-OH),4.02(s,2H,-CH2-),4.85(s,1H,),4.96(s,1H,)；IR(KBr):3093,2729,1662,1293,1179,949,820,660cm
-1。
EI-MS(75eV):m/z(%)80(26),65(14,[M-CH
3]
+),63(80,[M-OH]
+),56(96),41(100)。
Embodiment 2
The preparation method of 2-methallyl alcohol, is shown in Fig. 3, comprises the following steps:
1, under room temperature 25 DEG C of conditions, by iso-butylene: water vapour: the volume ratio charging of air=8:8:84, Feed space velocities 3000h
-1, the catalyst A molecular formula of fixed-bed reactor filling is: Mo
13.6bi
0.6co
6fe
1.8cs
0.2b
0.2o
g, temperature of reaction is 380 DEG C, and reactor thief hole samples, chromatography of gases detects, and when iso-butylene≤0.1%, 2-methallyl aldehyde>=98.0%, shows to react completely, discharging enters condenser, gas-liquid separator successively, and the aqueous solution of isolated 2-methallyl aldehyde enters next step reaction unit.
2, plant hydrogen first purges the fixed-bed reactor being filled with catalyst B, catalyst B molecular formula: Ir-ReOx/SiO
2-1, the then aqueous solution of charging 2-methallyl aldehyde, the volume ratio controlling methacrolein and water is 0.8, is filled with H in plant hydrogen to reactor
2pressure keeps 1.0MPa, keeps air speed 6h
-1temperature of reaction 90 DEG C, gas chromatographic detection, 2-methallyl aldehyde≤0.1%, 2-methallyl alcohol>=98.0%, show to react completely, material enters condenser, gas-liquid separator, isolated hydrogen circulates, liquid material is pumped to the rectifying tower that 16 pieces of stage number are housed and purifies, and is slowly warming up to 150 DEG C, keeps reflux ratio 1.5, selection 100 ~ 120 DEG C, the content of 2-methallyl alcohol can reach 98%, comprehensively accounts, and the yield of two-step reaction 2-methallyl alcohol is 88%, selection rate is 92%.
Product structure characterization data is close with embodiment 1.
Embodiment 3
The preparation method of 2-methallyl alcohol, is shown in Fig. 3, comprises the following steps:
1, under room temperature 25 DEG C of conditions, by iso-butylene: water vapour: the volume ratio charging of air=4:4:92, Feed space velocities 6000h
-1, the catalyst A molecular formula of fixed-bed reactor filling is: Mo
13.6bi
0.6co
6fe
1.8cs
0.2b
0.2o
g, temperature of reaction is 340 DEG C, and reactor thief hole samples, chromatography of gases detects, and when iso-butylene≤0.1%, 2-methallyl aldehyde>=98.0%, shows to react completely, discharging enters condenser, gas-liquid separator successively, and the aqueous solution of isolated 2-methallyl aldehyde enters next step reaction unit.
2, plant hydrogen first purges the fixed-bed reactor being filled with catalyst B, catalyst B molecular formula: Ir-ReOx/SiO
2-1, the then aqueous solution of charging 2-methallyl aldehyde, the volume ratio controlling methacrolein and water is 1.0, is filled with H in plant hydrogen to reactor
2pressure keeps 0.4MPa, keeps air speed 6h
-1temperature of reaction 70 DEG C, gas chromatographic detection, 2-methallyl aldehyde≤0.1%, 2-methallyl alcohol>=98.0%, show to react completely, material enters condenser, gas-liquid separator, isolated hydrogen circulates, liquid material is pumped to the rectifying tower that 16 pieces of stage number are housed and purifies, and is slowly warming up to 150 DEG C, keeps reflux ratio 1.5, selection 100 ~ 120 DEG C, the content of 2-methallyl alcohol can reach 98%, comprehensively accounts, and the yield of two-step reaction 2-methallyl alcohol is 90%, selection rate is 94%.
Product structure characterization data is close with embodiment 1.
Embodiment 4
The preparation method of 2-methallyl alcohol, is shown in Fig. 3, comprises the following steps:
1, under room temperature 25 DEG C of conditions, by iso-butylene: water vapour: the volume ratio charging of air=5:5:90, Feed space velocities 5000h
-1, the catalyst A molecular formula of fixed-bed reactor filling is: Mo
13.6bi
0.6co
6fe
1.8cs
0.2b
0.2o
g, temperature of reaction is 350 DEG C, and reactor thief hole samples, chromatography of gases detects, and when iso-butylene≤0.1%, 2-methallyl aldehyde>=98.0%, shows to react completely, discharging enters condenser, gas-liquid separator successively, and the aqueous solution of isolated 2-methallyl aldehyde enters next step reaction unit.
2, plant hydrogen first purges the fixed-bed reactor being filled with catalyst B, catalyst B molecular formula: Ir-ReOx/SiO
2-1, the then aqueous solution of charging 2-methallyl aldehyde, the volume ratio controlling methacrolein and water is 1.1, is filled with H in plant hydrogen to reactor
2pressure keeps 0.5MPa, keeps air speed 5h
-1temperature of reaction 80 DEG C, gas chromatographic detection, 2-methallyl aldehyde≤0.1%, 2-methallyl alcohol>=98.0%, show to react completely, material enters condenser, gas-liquid separator, isolated hydrogen circulates, liquid material is pumped to the rectifying tower that 16 pieces of stage number are housed and purifies, and is slowly warming up to 150 DEG C, keeps reflux ratio 1.5, selection 100 ~ 120 DEG C, the content of 2-methallyl alcohol can reach 98%, comprehensively accounts, and the yield of two-step reaction 2-methallyl alcohol is 89%, selection rate is 93%.
Product structure characterization data is close with embodiment 1.
Embodiment 5-10
Concrete steps are with embodiment 1, and change the conditions such as input material volume ratio, air speed, temperature of reaction, other conditions are identical with embodiment 1, and concrete outcome is in table 1.
The conditions such as table 1 input material volume ratio, air speed, temperature of reaction are on the impact of reaction yield
Each product structure characterization data is close with embodiment 1.
Comparative example 1
Process is proceeded as follows with the continuous reaction apparatus shown in Fig. 3.
1, under room temperature 25 DEG C of conditions, by iso-butylene: the volume ratio charging of air=8:92, Feed space velocities 5000h
-1, the catalyst A molecular formula of fixed-bed reactor filling is: Mo
12bi
0.6co
6fe
1.8cs
0.2b
0.2o
gtemperature of reaction is 360 DEG C, reactor thief hole samples, chromatography of gases detects, 2-methallyl aldehyde≤70.0%, reduce air speed or extend the reaction times, the content of 2-methallyl aldehyde cannot promote, discharging enters condenser, gas-liquid separator successively, and the aqueous solution of isolated 2-methallyl aldehyde enters next step reaction unit.
2, plant hydrogen first purges the fixed-bed reactor being filled with catalyst B, catalyst B molecular formula: Ir-ReOx/SiO
2-1, the then aqueous solution of charging 2-methallyl aldehyde, the volume ratio controlling methacrolein and water is 1.0, is filled with H in plant hydrogen to reactor
2pressure keeps 0.8MPa, keeps air speed 5h
-1temperature of reaction 80 DEG C, gas chromatographic detection, 2-methallyl aldehyde≤0.1%, 2-methallyl alcohol>=98.0%, show to react completely, material enters condenser, gas-liquid separator, isolated hydrogen circulates, liquid material is pumped to the rectifying tower that 16 pieces of stage number are housed and purifies, and is slowly warming up to 150 DEG C, keeps reflux ratio 1.5, selection 100 ~ 120 DEG C, the content of 2-methallyl alcohol can reach 98%, comprehensively accounts, and the yield of two-step reaction 2-methallyl alcohol is 68%, selection rate is 82%.
Product structure characterization data is the same close.
From this comparative example: be filled with water vapour in reactions steps 1 very crucial for the selectivity of the efficiency and 2-methallyl aldehyde that improve oxidizing reaction.
Comparative example 2
1, under room temperature 25 DEG C of conditions, by iso-butylene: water vapour: the volume ratio charging of air=8:8:84, Feed space velocities 5000h
-1, the catalyst A molecular formula of fixed-bed reactor filling is: Mo
12bi
0.6co
6fe
1.8cs
0.2b
0.2o
g, temperature of reaction is 360 DEG C, and reactor thief hole samples, chromatography of gases detects, and when iso-butylene≤0.1%, 2-methallyl aldehyde>=98.0%, shows to react completely, discharging enters condenser, gas-liquid separator successively, and the aqueous solution of isolated 2-methallyl aldehyde enters next step reaction unit.
2, plant hydrogen first purges the fixed-bed reactor being filled with catalyst B, catalyst B molecular formula: Ir-ReOx/SiO
2-1, the then aqueous solution of charging 2-methallyl aldehyde, the volume ratio controlling methacrolein and water is 1.0, is introduced into solution separating device, gets the organic layer charging of upper strata 2-methallyl aldehyde, be filled with H in plant hydrogen to reactor
2pressure keeps 0.8MPa, keeps air speed 5h
-1temperature of reaction 80 DEG C, gas chromatographic detection, 2-methallyl aldehyde≤0.1%, 2-methallyl alcohol>=98.0%, show to react completely, material enters condenser, gas-liquid separator, isolated hydrogen circulates, liquid material is pumped to the rectifying tower that 16 pieces of stage number are housed and purifies, and is slowly warming up to 150 DEG C, keeps reflux ratio 1.5, selection 100 ~ 120 DEG C, the content of 2-methallyl alcohol can reach 98%, comprehensively accounts, and the yield of two-step reaction 2-methallyl alcohol is 70%, selection rate is 92%.
Product structure characterization data is the same close.
From this comparative example: the water in reactions steps 2 in material is very crucial to the efficiency of reduction reaction.
Claims (3)
1. a preparation method for 2-methallyl alcohol, is characterized in that: comprise the following steps:
(1) under catalyst A, water vapour and air exist, iso-butylene is oxidized to 2-methallyl aldehyde; The volume ratio of iso-butylene, water vapor and air is (4:4:92)-(8:8:84);
The structural formula of described catalyst A is: Mo
a-Bi
b-M
iI c-M
iII d-M
i e-X
f-O
g;
Wherein,
M
iIbe selected from Ni
2+, Co
2+, Mg
2+, Mn
2+, Cu
2+and Pb
2+in 1 to 3 kind;
M
iIIbe selected from Fe
3+, Cr
3+, Al
3+in 1 to 3 kind;
M
ibe selected from K
+, Na
+, Cs
+1 to 3 kind in alkalimetal ion;
X is P or B;
A=12+ (1.6-4.0), b=0.1-0.8, c=5-8, d=1.0-2.8, e=0-0.4, f=0-0.4, g are the numerical value meeting other element oxide state;
(2) under catalyst B, hydrogen exist, 2-methacrylic aldehyde is reduced to 2-methallyl alcohol in water; The volume ratio of 2-methallyl aldehyde and water is 0.8-1.2;
The structural formula of described catalyst B is M-ReOx/SiO
2-n;
Wherein,
M is selected from 1 to 2 kind in Ir, Rh, Pd, Ru and Pt;
N represents Re/M value, n=0.8-1.2; The oxidation state of x representative element Re.
2. the preparation method of a kind of 2-methallyl alcohol according to claim 1, it is characterized in that: in step (1), oxidizing reaction temperature is 320-380 DEG C, and oxidizing reaction air speed is 3000-6000h
-1.
3. the preparation method of a kind of 2-methallyl alcohol according to claim 1, it is characterized in that: in step (2), reduction reaction temperature is 60-90 DEG C, reduction reaction system pressure 0.4-1.0MPa, reduction reaction air speed 3-6h
-1.
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| CN106631691A (en) * | 2016-12-08 | 2017-05-10 | 上海华谊（集团）公司 | Method for preparing methallyl alcohol through acrylaldehyde selective hydrogenization |
| CN107365245B (en) * | 2017-07-10 | 2018-12-11 | 中国化学赛鼎宁波工程有限公司 | A kind of methallyl alcohol production system and method |
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